Large-scale synthesis and characterization of carbon spheres prepared by direct pyrolysis of hydrocarbons

Large-scale production of pure carbon spheres, with diameters from 50 nm to 1 μm, has been achieved via direct pyrolysis of a wide range of hydrocarbons, including styrene, toluene, benzene, hexane, cyclohexane and ethene, in the absence of catalyst. Specific systematic studies using styrene as the feedstock indicate that the sizes of the resulting of carbon nanospheres can be controlled quite well by adjusting the experimental conditions. The resulting materials have been fully characterized using SEM, TEM, AFM, HRTEM, EDX, elemental analysis, density measurement, XPS, FTIR, XRD, Raman, and TGA. The results show that the spheres, which are 99% carbon, consist of concentric incompletely closed graphitic shells. The dangling bonds on the edges of the shells result in high chemical reactivity.     

Probing the evolution and morphology of hard carbon spheres

Monodispersed hard carbon spheres can be synthesized quickly and reproducibly by autogenic reactions of hydrocarbon precursors, notably polyethylene (including plastic waste), at high temperature and pressure. The carbon microparticles formed by this reaction have a unique spherical architecture, with a dominant internal nanometer layered motif, and they exhibit diamond-like hardness and electrochemical properties similar to graphite. In the present study, in situ monitoring by X-ray diffraction along with electron microscopy, Raman spectroscopy, neutron pair-distribution function analysis, and computational modeling has been used to elucidate the morphology and evolution of the carbon spheres that form from the autogenic reaction of polyethylene at high temperature and pressure. A mechanism is proposed on how polyethylene evolves from a linear chain-based material to a layered carbon motif. Heating the spheres to 2400–2800 °C under inert conditions increases their graphitic character, particularly at the surface, which enhances their electrochemical and tribological properties.     

High resolution transmission electron microscopy study on polyacrylonitrile/carbon nanotube based carbon fibers and the effect of structure development on the thermal and electrical conductivities

Polyacrylonitrile (PAN) and PAN/carbon nanotube (CNT) based carbon fibers at various CNT content have been processed and their structural development was investigated using high resolution transmission electron microscope (HR-TEM). In CNT containing carbon fibers, the CNTs act as templating agents for the graphitic carbon structure development in their vicinity at the carbonization temperature of 1450 °C, which is far below the graphitization temperature of PAN based carbon fiber (>2200 °C). The addition of 1 wt% CNT in the gel spun precursor fiber results in carbon fibers with a 68% higher thermal conductivity when compared to the control gel spun PAN based carbon fiber, and a 103% and 146% increase over commercially available IM7 and T300 carbon fibers, respectively. The electrical conductivity of the gel spun PAN/CNT based carbon fibers also showed improvement over the investigated commercially available carbon fibers. Increases in thermal and electrical conductivities are attributed to the formation of the highly ordered graphitic structure observed in the HR-TEM images. Direct observation of the graphitic structure, along with improved transport properties in the PAN/CNT based carbon fiber suggest new applications for these materials.     

Surface-modified carbons as platinum catalyst support for PEM fuel cells

Carbon forms, such as activated carbon, carbon black, carbon nanofibers and nanotubes, can be used as support materials for precious metal catalysts used in fuel cell electrodes. This work first compares the ability of functionalized high surface area graphitic (carbon nanofibers) and amorphous (activated carbon) carbons to homogeneously support finely divided platinum catalyst particles, then contrasts the performance of platinum/carbon composite electrodes within a hydrogen fuel cell. Functionalization by concentrated acid treatment results in the creation of various oxygen carrying functionalities on the otherwise inert carbon surfaces. The degree of surface functionalization is found to be a function of the functionalization treatment strength. Chemical reduction of the platinum precursor complex using milder reducing agents in the temperature range of 75-85 °C, and using ethylene glycol at 140 °C yields the smallest platinum particle sizes observed in this study, a result confirmed by X-ray diffraction and transmission electron microscopy measurements. X-ray photoelectron spectroscopy measurements confirm the existence of platinum in primarily its metallic state on the functionalized carbon surfaces.     

Mechanism for the preparation of carbon spheres from potato starch treated by NH4Cl

Carbon spheres (CSs) retaining the morphology of potato starch were prepared by a two-step process: impregnation followed by carbonization. In this process, potato starch was impregnated in NH₄Cl solution for 1 h. The mechanism of preparation was proposed. The presence of HCl catalyzes the dehydration of impregnated starch at lower temperature than its melting point, which destroys the crystallites in original starch totally. This makes the microcrystalline melting difficult during the following carbonization. Scanning electron microscopy results show that small cavity exists in the center of sphere. The CSs shows high graphitization degree after graphitizing by X-ray diffraction analysis.     

Nanodiamond crystallites embedded in carbon films prepared by thermionic vacuum arc method

Nanostructured carbon films with thicknesses of 100 and 200 nm have been deposited from pure vapour carbon plasma using an original thermionic vacuum arc method. Silicon single crystalline wafers, glass and stainless steel held at 400 °C were used for substrates. The films consist of diamond nanoparticles of 5 nm diameter on the average embedded in a disordered graphite matrix as revealed by HRTEM, XPS and visible Raman measurements. The graphitic cluster diameters La range from 1.5 to 2.3 nm. Thicker films (200 nm) on stainless steel exhibit the largest clusters.     

The influence of carbon spheres on thermal and mechanical properties of epoxy composites

In order to improve the properties of epoxy resion, a reinforcement addictive of carbon spheres (CSs) was successfully synthesized by hydrothermal methods and CSs/Epoxy composite was prepared using in-situ polymerization technique. The morphology and structure of CSs and CSs/Epoxy composites were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that CSs distributed homogeneously in epoxy matrix and the integrating state of interface between CSs and epoxy is good. TGA and DMA analysis showed that the thermal stability of CSs/Epoxy composite in air and the glass transition temperature (T_g) increased with the addition of CSs. DMA results show that the creep recovery property also improved. Additionally. The impact fracture strength of EP composites increased after the addition of CSs compared to pure EP, it means the toughness of epoxy improved effectively, which attribute to the effective dissipation of the crash energy. Finally, the mechanism for the improvement of mechanical properties by the CSs is also discussed.     

Highly porous carbon spheres for electrochemical capacitors and capacitive flowable suspension electrodes

In flowable and conventional electrochemical capacitors, the energy capacity is largely determined by the electrode material. Spherical active material, with high specific surface area (SSA) represents a promising material candidate for film and flow capacitors. In this study, we synthesized highly porous carbon spheres (CSs) of submicrometer size to investigate their performance in film and suspension electrodes. In particular, we studied the effects of carbonization and activation temperatures on the electrochemical performance of the CSs. The CSs activated at optimum conditions demonstrated narrow pore size distribution (<3 nm) with high SSA (2900 m²/g) and high pore volume (1.3 cc/g), which represent significant improvement as compared to similar materials reported in literature. Electrochemical tests of CSs in 1 M H₂SO₄ solution showed a specific capacitance of 154 F/g for suspension electrode and 168 F/g for film electrode with excellent rate performance (capacitive behaviors up to 100 mV/s) and cycling performance (95% of initial capacitance after 5000 cycles). Moreover, in the film electrode configuration, CSs exhibited high rate performance (78 F/g at 1000 mV/s) and volumetric power density (9000 W/L) in organic electrolytes, along with high energy density (21.4 Wh/L) in ionic liquids.     

Nanosized carbon forms in the processes of pressure-temperature-induced transformations of hydrocarbons

The products of thermal conversions of naphthalene, anthracene, pentacene, perylene, and coronene at 8 GPa in the temperature range up to 1300 °C have been studied by scanning electron and high-resolution transmission electron microscopies. As a result, it has been established that various nanometer-sized carbon species (spherical and coalesced two-core onion-like carbon particles, faceted polyhedral particles, graphitic ribbons, graphitic folds, and nanocrystalline diamonds) are present in the conversion products together with micron-sized crystallites of graphite and diamond.     

Characterization of silicon- and carbon-based composite anodes for lithium-ion batteries

In recent years development of active materials for negative electrodes has been of great interest. Special attention has been focused on the active materials possessing higher reversible capacity than that of conventional graphite. In the present work the electrochemical performance of some carbon/silicon-based materials has been analyzed. For this purpose various silicon-based composites were prepared using such carbon materials as graphite, hard carbon and graphitized carbon black. An analysis of charging-discharging processes at electrodes based on different carbon materials has shown that graphite modified with silicon is the most promising anode material. It has also been revealed that the irreversible capacity mainly depends on the content of Si. An optimum content of Si has been determined with taking into account that high irreversible capacity is not suitable for practical application in lithium-ion batteries. This content falls within the range of 8-10 wt%.The reversible capacity of graphite modified with 8 wt% carbon-coated Si was as high as 604 mAh g⁻¹. The irreversible capacity loss with this material was as low as 8.1%. The small irreversible capacity of the material allowed developing full lithium-ion rechargeable cells in the 2016 coin cell configuration. Lithium-ion batteries based on graphite modified with silicon show gravimetric and volumetric specific energy densities which are higher by approximately 20% than those for a lithium-ion battery based on natural graphite.     

Investigating the structure of biomass-derived non-graphitizing mesoporous carbons by electron energy loss spectroscopy in the transmission electron microscope and X-ray photoelectron spectroscopy

We have investigated the microstructure and bonding of two biomass-based porous carbon chromatographic stationary phase materials (alginic acid-derived Starbon® and calcium alginate-derived mesoporous carbon spheres (AMCS)) and a commercial porous graphitic carbon (PGC), using high resolution transmission electron microscopy, electron energy loss spectroscopy (EELS), N₂ porosimetry and X-ray photoelectron spectroscopy (XPS). The planar carbon sp²-content of all three material types is similar to that of traditional non-graphitizing carbon although, both biomass-based carbon types contain a greater percentage of fullerene character (i.e. curved graphene sheets) than a non-graphitizing carbon pyrolyzed at the same temperature. This is thought to arise during the pyrolytic breakdown of hexauronic acid residues into C5 intermediates. Energy dispersive X-ray and XPS analysis reveals a homogeneous distribution of calcium in the AMCS and a calcium catalysis mechanism is discussed. That both Starbon® and AMCS, with high-fullerene character, show chromatographic properties similar to those of a commercial PGC material with extended graphitic stacks, suggests that, for separations at the molecular level, curved fullerene-like and planar graphitic sheets are equivalent in PGC chromatography. In addition, variation in the number of graphitic layers suggests that stack depth has minimal effect on the retention mechanism in PGC chromatography.     

Porous nitrogen-doped carbon vegetable-sponges with enhanced lithium storage performance

Porous nitrogen-doped carbon vegetable-sponges (N-DCSs) have been fabricated by chemical treatment of the Cu@C precursors using HNO₃ for the first time. The obtained N-DCSs are porous three-dimensional (3D)-structure and similar to numerous agglomerated fluffy micro-vegetable-sponges. When the precursors are treated by H₂SO₄, carbon vegetable-sponges (CSs) without nitrogen doping are prepared. As anode materials in lithium ion batteries, the as-prepared N-DCSs show improved Li-storage capacity and cycling stability as compared with the pure CSs. They offer 870 mA h g⁻¹ at 0.5 A g⁻¹ after 300 cycles and high reversible capacity with 910 mA h g⁻¹ at 0.2 A g⁻¹ after cycled at different current densities, which are much higher than those of CSs. It is envisaged that the large surface area, unique 3D porous nanostructure and appropriate nitrogen doping are favorable for the superior electrochemical properties of N-DCSs.     

Molten salt synthesis of nitrogen-doped porous carbons for hydrogen sulfide adsorptive removal

Nitrogen-doped porous carbons (NPCs) with high hydrogen sulfide (H₂S) adsorption capacity have been prepared through the molten-salt approach, using d-glucose as carbon source, melamine as nitrogen source and eutectic salt (LiCl/KCl) as porogen. The NPCs possess tunable nitrogen content (3.07–24.31 wt.%) and specific surface area (451–1190 m²/g) with the changing of the weight ratio of nitrogen source to carbon source and synthesis temperature. The H₂S adsorptive performance of NPCs is highly superior to that of non-doped porous carbon. X-rays photoelectron spectroscopy analyses combined with quantum chemical calculations demonstrate that the adsorption performance of the as-prepared NPCs depends on their nitrogen content and N-bonding configurations in the carbon materials, as well as their porosity. Pyridinic nitrogen doped carbon in NPCs have stronger interaction with H₂S compared to pyrrolic and graphitic nitrogen doped carbon. Based on the advantages of the developed porosity and abundant nitrogen functional groups, the saturated sorption capacities of 0.97–1.25 mmol H₂S/g can be achieved over NPCs at 25 °C under dry and anaerobic conditions.     

Structural evolution of carbon microcoils induced by a direct current

The structural evolution of a carbon microcoil (CMC) induced by a direct current was studied using a scanning tunneling microscope-transmission electron microscope work station. We found that the CMC got broken when a high-density current was passed through, and it was partially transformed into hollow graphitic spheres, double-walled carbon nanotubes, and fullerenes. A transformation process involving pore formation, high temperature induced graphitization, and closure of dangling bonds is proposed. The driving force of the structural evolution is considered to be the high temperature effect and electromigration effect brought by the current, and the graphitic crystallites composing the CMCs tend to reconstruct to form carbon nanomaterials with enhanced structural integrity when a high-density direct current is applied.     

Spontaneous, catalyst-free formation of nitrogen-doped graphitic carbon nanocages

A simple approach for spontaneous, catalyst-free formation of highly graphitic nitrogen-containing carbon nanocages has been demonstrated by using commercially available graphite rods as the initial materials. The resultant carbon nanocages have well-ordered graphitic shells with more compact graphite layer structure than that of conventional bulk graphite. The incorporation of nitrogen into the graphitic backbone of carbon nanocages opens the potential for metal-free catalysis of oxygen reduction reaction in fuel cells. It is believed that the formation of carbon nanocages were attributed to the incurvature and coalescence of graphite sheets shelled off from graphite rods. Thermal gravimetric analysis revealed the as-prepared carbon nanocages possessed excellent thermal stability in both N₂ (1200 °C) and air (700 °C) atmospheres promising for applications in high-temperature environments.     

Modeling initial stage of phenolic pyrolysis: Graphitic precursor formation and interfacial effects

Reactive molecular dynamics simulations are used to study the initial stage of pyrolysis of phenolic polymers with carbon nanotube and carbon fiber. The products formed are characterized and water is found to be the primary product in all cases. The water formation mechanisms are analyzed and the value of the activation energy for water formation is estimated. A detailed study of graphitic precursor formation reveals the presence of two temperature zones. In the lower temperature zone (<2000 K) polymerization occurs resulting in the formation of large, stable graphitic precursors, while in the high temperature zone (>2000 K) polymer scission results in formation of short polymer chains/molecules. Simulations performed in the high temperature zone of the phenolic resin (with carbon nanotubes and carbon fibers) show that the presence of interfaces does not have a substantial effect on the chain scission rate or the activation energy value for water formation.     

Surface modification of carbonaceous materials for EDLCs application

In this study, carbonaceous materials such as activated carbon and activated carbon aerogel were chemically modified with a surfactant sodium oleate in order to improve their specific capacitance and energy storage in electrochemical double-layer capacitors (EDLCs). Optimal conditions for surface modification of activated carbon have been examined as a surfactant solution concentration of 0.25 wt.% together with a time of 24 h for treatment at 25 °C. Specific capacitance and energy density can be improved significantly by surface modification of carbon materials. The enhancement in specific capacitance and energy density is mainly attributable to improvement in wettability of carbon materials, which results in a higher usable surface area and a smaller internal resistance. The effects from surface modification become more marked at higher discharge rates, at which the internal resistance has a more important impact on the energy delivery. A two times energy density of the original carbon could be achieved for the modified carbon materials at a high discharge rate, which indicates that the modified carbons are more suitable in EDLCs for high current applications. In addition, the modified carbon materials possess excellent cycle stability (the capacity decay was only 4% after 20,000 cycles).     

Electron microscopy profiling of ion implantation damage in diamond: Dependence on fluence and annealing

The doping of diamond by ion implantation has been feasible for 25 years, but with the proviso that low dose implants can be annealed whereas high dose implants “graphitize”. An understanding of the types of defects, and their depth profiles, produced during the doping/implantation of diamond remains essential for the optimization of high-temperature, high-power electronic applications. This study focuses on investigating the nature of the radiation damage produced during the implantation of carbon ions into synthetic type Ib and natural diamonds using a spread of 4 energies, corresponding to typical doping energies, according to the CIRA (Cold-Implantation-Rapid-Annealing) routine, as well as a single energy implantation at room temperature. Both conventional and high resolution cross-sectional electron microscopies were achieved and used to analyze the implanted diamonds in conjunction with electron energy loss spectroscopy (EELS) and selected area diffraction (SAD). The cross sections were obtained using two different preparation methods.For low fluence implantations, using the CIRA routine, it is confirmed that the damaged diamond regains its crystallinity after annealing at 1600 K. However, above the amorphization threshold fluence, followed by rapid annealing at 1600 K, the whole implanted layer consisted of primarily amorphous carbon. High resolution TEM shows that the implanted layer consists of nano-regions with bent (002) graphitic planes and regions of amorphous carbon. The interface between the implanted layer and the diamond substrate near end of range shows diamond nanocrystallites, interspersed between regions of amorphous carbon and with bent (002) graphitic planes. There is no evidence for epitaxial regrowth. For high dose single energy ion implantation at room temperature, the unannealed layer shows a high degree of disorder at the maximum ion range, with some alignment of basal planes related to graphitic carbon, but with some of the diamond structure still partially intact. The implanted range included a diamond layer above the damaged region. This diamond layer showed no evidence of amorphous carbon.     

Electrochemical performance of pyrolytic carbon-coated natural graphite spheres

Natural graphite (NG) spheres were coated by pyrolytic carbon from the thermal decomposition of C₂H₂/Ar at 950 °C in a fluidized bed reactor. Scanning electron microscopy and secondary electron focused ion beam (FIB) images clearly showed that a pyrolytic carbon layer with a thickness of ∼250 nm was uniformly deposited on the surface of the NG spheres. Electrochemical performance measurements for the original and coated NG spheres as anode materials of a lithium-ion battery indicated that the first coulombic efficiency and cyclability were significantly improved in the coated sample. The reasons for this were investigated by analyzing structural characteristics, specific surface area, pore size distribution, and solid electrolyte interphase (SEI) film. Using a FIB workstation, we demonstrated, by cross-section imaging of a coated NG sphere that had experienced five electrochemical cycles, that the SEI film formed on the non-graphitic pyrolytic carbon surface became thinner (60-150 nm) and more uniform in composition compared with that on the surface of uncoated NG spheres; and the formation of an “internal SEI film” inside the NG spheres was also remarkably suppressed due to the uniform coating of pyrolytic carbon.     

Textural property tuning of ordered mesoporous carbon obtained by glycerol conversion using SBA-15 silica as template

“Wet” and “dry” template methods were used to simultaneously control the pore size, morphology, and graphitization in structurally well-ordered mesoporous carbons. A novel structure has been prepared using glycerol as the carbon source. Depending on the loading amount of the glycerol, the structural characteristics of the mesoporous carbon materials can be controlled. The structurally well-ordered carbon materials have been characterized by various techniques such as nitrogen sorption, XRD, Raman spectroscopy, TGA measurements and SEM. They have graphitic character, high BET surface area (ca 1440 m²/g) and a tunable pore size. They are likely to be useful in a variety of applications including gas storage, electrode materials or catalyst supports.